Processing materials

ABSTRACT

Biomass (e.g., plant biomass, animal biomass, and municipal waste biomass) is processed to produce useful products, such as fuels. For example, systems are described that can use feedstock materials, such as cellulosic and/or lignocellulosic materials and/or starchy materials, to produce ethanol and/or butanol, e.g., by fermentation. Hydrocarbon-containing materials are also used as feedstocks.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 61/109,159, filed Oct. 28, 2008. The complete disclosure of thisprovisional application is hereby incorporated by reference herein.

BACKGROUND

Biomass, particularly biomass waste, is abundantly available. It wouldbe useful to derive materials and fuel, such as ethanol, from biomassand other materials.

SUMMARY

Materials can be processed to alter their structure at one more levels.The processed materials can then be used as a source of other materialsand fuel.

Many embodiments of this application use Natural Force™ Chemistry (NFC).Natural Force™ Chemistry methods use the controlled application andmanipulation of physical forces, such as particle beams, gravity, light,etc., to create intended structural and chemical molecular change. Byapplying the processes of Nature, new useful matter can be createdwithout harmful environmental interference. The present applicationdescribes new feedstock preparation methods that include combininginorganic additives with materials, such as biomass, hydrocarbons orcoal, to modulate, e.g., enhance, the effect on the biomass of variousphysical forces, such as particle beams and other forms of radiation.

Methods described herein for changing a molecular and/or asupramolecular structure of any biomass material include treating thebiomass material with radiation after the addition of inorganicadditives, such as one or more ceramics, and/or one or more metals,and/or one or more refractive materials, and/or one or more clays,and/or one or more minerals. In particular, the radiation can includebeams of particles, particularly charged particles, such as beams ofelectrons. Charged particles include ions, such as positively chargedions, e.g., protons, carbon or oxygen ions. In some cases, the chargedparticles can be heavier than an electron or have a different chargethan an electron (e.g., a positron). The radiation can be applied in anamount sufficient to change the molecular structure and/orsupramolecular structure of the biomass material.

Other materials, such as hydrocarbon-containing materials, e.g.,hydrocarbons and coal can be processed in an analogous manner. When coalis utilized, it can be in solid form, e.g, pulverized coal, or it can bein liquefied form. Coal can be liquified by a number of techniques, suchas by the Bergius process, the SRC-I and SRC-II (Solvent Refined Coal)processes and the NUS Corporation hydrogenation process. When coal isutilized, it can be lignite, flame coal, gas flame coal, fat coal, forgecoal, non-baking coal, anthracite coal or mixtures of any one or more ofthese types of coal.

For example, protons, helium nuclei, argon ions, silicon ions, neonions, carbon ions, phosphorus ions, oxygen ions or nitrogen ions can beutilized to modify the structure of the biomass, e.g., breakdown themolecular weight or increase the molecular weight of the biomass. Insome embodiments, heavier particles can induce higher amounts of chainscission in comparison to electrons or photons. In addition, in someinstances, positively charged particles can induce higher amounts ofchain scission than negatively charged particles due to their acidity.

The material resulting from irradiating the combination can be used inany suitable application, such as any of those described herein, e.g.,for fuel, food, or as use in composite materials. For example, some ofthe methods described herein further include removing the inorganicmaterial, and then contacting the resulting material with an enzymeand/or a microorganism for a time and under conditions sufficient toconvert the carbohydrate-containing material to a fuel, such as ethanolor butanol (e.g., n-butanol). In other embodiments, the method furtherincludes contacting the combination with an enzyme and/or amicroorganism for a time and under conditions sufficient to convert thecarbohydrate-containing material to a fuel, such as ethanol or butanol.In some embodiments, the methods include contacting the treated biomassmaterial (with or without the inorganic material) with an enzyme tosaccharify the material, and then inoculating the saccharified materialwith a microorganism to make a useful product, such as a fuel, such asethanol, butanol or a hydrocarbon. If desired, the inorganic materialcan be separated and utilized again in the irradiating process.

In certain aspects, the invention features methods of making acarbohydrate-containing material that include combining a cellulosicand/or lignocellulosic material with an inorganic material, such as ametal or a metallic compound, a refractory material, a ceramic ormixtures of any of these, to provide a combination; and irradiating thecombination. Irradiation may be, for example, with acceleratedparticles, such as electrons, e.g., at a speed of greater than seventyfive percent of the speed of light.

In some implementations, the cellulosic or lignocellulosic materials canbe selected from the group consisting of paper, paper products, wood,wood-related materials, such as sawdust and particle board, grasses,such as straw and switchgrass, rice hulls, bagasse, alfalfa, hay,cotton, jute, hemp, flax, bamboo, sisal, abaca; agricultural wastes,such as corn cobs, corn stover, bagasse and coconut hair; algae,seaweed, sewage, silage, synthetic celluloses, extruded yarn scraptextile materials, rags, and mixtures thereof.

The cellulosic and/or lignocellulosic and inorganic materials can becombined, for example, by dry blending or by co-comminuting thecellulosic and/or lignocellulosic material and inorganic materialstogether. Co-comminution can be performed while each material is cooled,e.g., to a temperature below 25° C., 0° C., the normal atmosphericsublimation temperature of dry ice, or even at or below the normalatmospheric boiling point of liquid nitrogen.

In certain embodiments, the inorganic material can be or include a metalor a metal alloy, e.g., a base metal, such as iron, nickel, lead,copper, or zinc, or a ferrous metal such as wrought iron or pig iron, ora noble metal, such as tantalum, gold, platinum, or rhodium. The metalor metal alloy can also be or include a precious metal, such asruthenium, rhodium, palladium, osmium, iridium or platinum, or atransition metal. The metal alloy can be, e.g., steel, brass, bronze,duralumin, or hastaloy. The metal can be aluminum. In certainembodiments, the inorganic material can be or include a metalliccompound, such as inorganic compound of iron or cobalt, and theinorganic compound can be in the 2+ or 3+ oxidation state.

In other embodiments, the inorganic material can be or include arefractory material, such as an acidic, neutral, or basic refractorymaterial. The acid refractory material can be zircon, fireclay, orsilica. The neutral refractory material can be alumina, chromite,silicon carbide, carbon, or mulitite. The basic refractory material canbe or include dolomite or magnesite.

In some embodiments, the inorganic material can be or include a ceramic,such as an oxide, a carbide, a boride, a nitride, a silicide, or akaolin, and the oxide can be or include an aluminum oxide, such asalumina, a zirconium oxide, a silicon oxide, a zinc oxide, or a titaniumoxide, such as titanium dioxide.

In certain embodiments, the inorganic material includes water that iscapable of leaving the inorganic material at elevated temperatures, suchas hydrated alumina. In some embodiments, the inorganic material doesnot have a melting point. In other embodiments, the inorganic materialhas a melting point of greater than about 400° C., such as greater thanabout 500, 600, 700, 800, 900, 1000, 1200, 1,400, 1600, 1800, 2000,2200, 2400, 2600 or even greater than 2800° C.

The inorganic materials useful in the methods described herein can havea specific heat capacity Cp of less than about 1.5, such as less thanabout 1.25, 1.0, 0.75, 0.50, 0.25 or even less than about 0.1 J/gK. Forexample, the inorganic materials can have a specific heat capacity Cp ofbetween about 1.25 and about 0.2 J/gK, such between about 1.15 and about0.25 or between about 0.85 and 0.30 J/gK. In addition, the inorganicmaterials can have a conductivity of between about 0.004 and about 450W/mK, between about 0.04 and about 250 W/mK, between about 0.1 and about150 or between about 0.25 and about 50 W/mK, and a density of greaterthan about 1.5 g/cm³, such as greater than about 2.0, 2.5, 3.0, 5.0,7.0, 8.0, 9.0, 12.0, 15.0, 18.0, or even greater than 20.0 g/cm³. Inother embodiments, the inorganic material has a density of between about3.5 g/cm³ and about 20.0 g/cm³, between about 4.0 g/cm³ and about 18g/cm³ or between about 4.5 g/cm³ and about 13 g/cm³.

In certain embodiments, the inorganic materials can be in the form ofparticles that are substantially spherical in shape, and the averageparticle size can range from about 0.1 micron to about 100 microns, fromabout 0.25 micron to about 75 microns or from about 0.5 micron to about50 microns.

The irradiating of the combination can include subjecting thecombination to accelerated electrons, such as electrons having an energyof greater than about 2 MeV, 4 MeV, 6 MeV or even greater than about 8MeV.

In some embodiments, the combination includes about 0.05 to about 35,about 0.1 to about 20, or about 0.5 to about 10 percent by weightinorganic material.

Some methods further include contacting the irradiated cellulosic and/orlignocellulosic material, with or without first removing the inorganicmaterial, with an enzyme and/or a microorganism for a time and underconditions sufficient to convert the carbohydrate-containing material toa fuel, such as ethanol or butanol.

In another aspect, the invention features compositions of matter thatinclude in combination, e.g., in homogeneous combination, a particulatecarbohydrate-containing material and a particulate inorganic material,such as a metal or a metallic compound, a refractory material, a ceramicor mixtures of any of these.

Generally, the inorganic material is exogenous to thecarbohydrate-containing material. The composition of matter can include,for example, at least about 0.5 percent by weight inorganic material,such as at least about 1, 3, 5, 10 or 25 percent by weight inorganicmaterial, or between about 0.5 and about 25 percent by weight inorganicmaterial, or between about 1 and about 15 percent by weight inorganicmaterial.

The methods for making and processing materials from biomass can includefunctionalizing biomass. In some instances, functionalized biomass ismore soluble and is more readily utilized by microorganisms incomparison to biomass that has not been functionalized. In addition,many of the functionalized materials described herein are less prone tooxidation and can have enhanced long-term stability (e.g., oxidation inair under ambient conditions).

In some implementations, the biomass feedstock is prepared by shearing abiomass fiber source to provide a fibrous material. For example, theshearing can be performed with a rotary knife cutter. The fibers of thefibrous material can have, e.g., an average length-to-diameter ratio ofgreater than 5/1. The fibrous material can have, e.g., a BET surfacearea of greater than 0.25 m²/g. In some cases, the biomass can have abulk density of less than about 0.35 g/cm³. Low bulk density materialscan be deeply penetrated by charged particles. For example, forelectrons at an average energy of 5 MeV and a material with a bulkdensity of 0.35 g/cm³, electron penetration depths can be 5-7 inches ormore.

In another aspect, the invention features a method of processing ahydrocarbon-containing material, the method including irradiating acombination formed by combining a hydrocarbon-containing material withan inorganic material.

In some aspects, the hydrocarbon-containing material is selected fromthe group consisting of tar or oil sands, oil shale, crude oil, bitumen,coal, petroleum gases, liquefied natural and/or synthetic gas, andasphalt.

Combinations (e.g., blends) of hydrocarbon-containing materials, e.g.,hydrocarbons and coal, and biomass can be processed in an analogousmanner.

When a microorganism is utilized in the processes described herein, itcan be a natural microorganism or an engineered microorganism. Forexample, the microorganism can be a bacterium, e.g., a cellulolyticbacterium, a fungus, e.g., a yeast, a plant or a protist, e.g., analgae, a protozoa or a fungus-like protist, e.g., a slime mold. When theorganisms are compatible, mixtures may be utilized. Generally, variousmicroorganisms can produce a number of useful products, such as a fuel,by operating on, e.g., fermenting the materials. For example,fermentation or other processes can be used to produce alcohols, organicacids, hydrocarbons, hydrogen, proteins, or mixtures of any of thesematerials.

Examples of products that may be produced include mono- andpolyfunctional C1-C6 alkyl alcohols, mono- and poly-functionalcarboxylic acids, C1-C6 hydrocarbons, and combinations thereof. Specificexamples of suitable alcohols include methanol, ethanol, propanol,isopropanol, butanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, and combinations thereof. Specific example of suitablecarboxylic acids include formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, palmitic acid, stearic acid,oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid,linoleic acid, glycolic acid, lactic acid, γ-hydroxybutyric acid, andcombinations thereof. Examples of suitable hydrocarbons include methane,ethane, propane, pentane, n-hexane, and combinations thereof. Many ofthese products may be used as fuels.

Changing a molecular structure of a biomass feedstock, as used herein,means to change the chemical bonding arrangement, such as the type andquantity of functional groups or conformation of the structure. Forexample, the change in the molecular structure can include changing thesupramolecular structure of the material, oxidation of the material,changing an average molecular weight, changing an average crystallinity,changing a surface area, changing a degree of polymerization, changing aporosity, changing a degree of branching, grafting on other materials,changing a crystalline domain size, or an changing an overall domainsize.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of the present invention, suitable methods andmaterials are described below. All publications, patent applications,patents, and other references mentioned herein are incorporated byreference in their entirety. In case of conflict, the presentspecification, including definitions, will control. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting.

This application incorporates by reference herein the entire contents ofInternational Application No. PCT/US2007/022719, filed Oct. 26, 2007;applications to which the aforementioned claims priority; Ser. Nos.61/049,391, 61/049,395, 61/049,419, 61/049,415, 61/049,413, 61/049,407,61/049,404, 61/049,394, and 61/049,405, each filed on Apr. 30, 2008.This application also incorporates by reference in their entireties thedisclosures of the U.S. patent applications having the following Ser.Nos. 12/486,436, 12/429,045, 12/417,904, 12/417,900, 12/417,880,12/417,840, 12/417,786, 12/417,731, 12/417,723, 12/417,720, 12/417,707,12/417,699, and 12/374,549.

The entire contents of each of the following publications areincorporated herein by reference: J. R. Adney et al., IEEE Transactionson Nuclear Science, Vol. NS-32, pp. 1841-1843 (1985); J. R. Adney etal., Proceedings of the 1989 IEEE Particle Accelerator Conference, Vol.1, pp. 348-350 (1989); J. A. Ferry et al., Nuclear Instruments andMethods in Physics Research, Vol. B64, pp. 309-312 (1992); J. Ferry, inHandbook of Accelerator Physics and Engineering, pp. 16-17 (1999); J. A.Ferry et al., Nuclear Instruments and Methods in Physics Research A,Vol. 382, pp. 316-320 (1996); J. A. Ferry, Nuclear Instruments andMethods in Physics Research A, Vol. 328, pp. 28-33 (1993); T. M. Hauseret al., Nuclear Instruments and Methods in Physics Research B, Vol. 249,pp. 932-934 (2006); R. G. Herb, in Encyclopedia of Physics, pp. 3-8(1981); R. G. Herb et al., in Encyclopedia of Applied Physics, Vol. 1,pp. 27-42 (1991); R. G. Herb, IEEE Transactions on Nuclear Science, Vol.NS-30, pp. 1359-1362 (1983); R. G. Herb, Proceedings of the ThirdInternational Conference on Electrostatic Accelerator Technology (1981);G. M. Klody et al., Nuclear Instruments and Methods in Physics ResearchB, Vol. 56-57, pp. 704-707 (1991); G. M. Klody et al., NuclearInstruments and Methods in Physics Research B, Vol. 240, pp. 463-467(2005); R. L. Loger, Application of Accelerators in Research andIndustry, Proceedings of the Fifteenth International Conference, pp.640-643 (1999); G. A. Norton et al., Nuclear Instruments and Methods inPhysics Research B, Vol. 40-41, pp. 785-789 (1989); G. A. Norton et al.,Application of Accelerators in Research and Industry, Proceedings of theFourteenth International Conference, pp. 1109-1114 (1997); G. Norton etal., Handbook of Accelerator Physics and Engineering, pp. 24-26 (1999);G. A. Norton et al., Symposium of North Eastern Accelerator Personnel,pp. 295-301 (1992); G. Norton, Pramana, Vol. 59, pp. 745-751 (2002); G.A. Norton et al., Nuclear Instruments and Methods in Physics Research B,Vol. 37-38, pp. 403-407 (1989); G. A. Norton, Heavy Ion AcceleratorTechnology: Eighth International Conference, pp. 3-23 (1999); J. E.Raatz et al., Nuclear Instruments and Methods in Physics Research A,vol. 244, pp. 104-106 (1986); R. D. Rathmell et al., Nuclear Instrumentsand Methods in Physics Research B, vol. 56-57, pp. 1072-1075 (1991); J.B. Schroeder et al., Nuclear Instruments and Methods in Physics ResearchB, Vol. 56-57, pp. 1033-1035 (1991); J. B. Schroeder, NuclearInstruments and Methods in Physics Research B, Vol. 40-41, pp. 535-537(1989); J. B. Schroeder et al., Radiocarbon, Vol. 46 (2004); J. B.Schroeder et al., Nuclear Instruments and Methods in Physics Research B,Vol. 24-25, pp. 763-766 (1987); P. H. Stelson et al., NuclearInstruments and Methods in Physics Research A, Vol. 244, pp. 73-74(1986); M. L. Sundquist et al., Nuclear Instruments and Methods inPhysics Research B, Vol. 99, pp. 684-687 (1995); M. L. Sundquist et al.,Nuclear Instruments and Methods in Physics Research A, Vol. 287, pp.87-89 (1990); and M. L. Sundquist, Applications of Accelerators inResearch and Industry, Proceedings of the Fifteenth InternationalConference, pp. 661-664 (1999). All other patents, patent applications,and references cited herein are also incorporated by reference.

Other features and advantages of the invention will be apparent from thefollowing detailed description, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 is a block diagram illustrating conversion of biomass intoproducts and co-products.

FIG. 2 is block diagram illustrating conversion of a fiber source into afirst and second fibrous material.

FIG. 3 is a cross-sectional view of a rotary knife cutter.

FIG. 4 is block diagram illustrating conversion of a fiber source into afirst, second and third fibrous material.

DETAILED DESCRIPTION

Systems and processes are described below that can use various biomassmaterials to form useful products. The biomass material is combined withone or more inorganic materials such as ceramics, metals, clays, and/orminerals and the combination is irradiated. The addition of theinorganic material modulates (increases/enhances or decreases) theeffects of the radiation on the biomass in comparison to applying thesame energy without the inorganic material being present. For example,the presence of the inorganic material can enhance the effect of theradiation on the biomass material by increasing the heat generated byirradiating.

For example, with the inorganic material present during irradiation, thedegree of recalcitrance of the cellulosic or lignocellulosic material tostructural change can be reduced to a greater extent for a givenradiation dose relative to the case in which the inorganic material isnot present during radiation treatment. For example, for any given dose,the average molecular weight and/or average crystallinity can be reducedby a greater degree, such as by 10, 20, 30, 40, 50, 60 or even 75percent greater, when a combination of biomass and inorganic material isirradiated in comparison to a radiation treatment of biomass without theinorganic material being present during the irradiation. For example,for any given dose, the surface area and/or the porosity of the biomasscan be increased by a greater degree, such as by 10, 20, 30, 40, 50, 60or even 75 percent greater, when a combination of biomass and inorganicmaterial is irradiated in comparison to the inorganic additive not beingpresent during the irradiation.

Without wishing to be bound by any particular theory, it is believedthat the inorganic additive can modulate the effects of the radiation onthe biomass through a number of potential mechanisms, including thermaleffects, activation effects (e.g., formation of reactive forms of theinorganic material), and secondary radiation effects (e.g.,bremsstrahlung x-rays). Thermal effects are believed to arise from theheating of the biomass by the inorganic material that is heated in theradiation field when the kinetic energy of the particles is converted toheat. Molecular activation effects are believed to arise from theconversion of the inorganic material into a more chemically activespecies, which in turn reacts directly with the biomass or with a gas,such as air in the radiation field. For example, in an embodiment inwhich titanium dioxide is present in the inorganic material, thetitanium dioxide can be activated in the radiation field to anelectronically excited form of titanium dioxide, which in turn can reactwith oxygen in the air to generate ozone about the biomass. Ozone canattack the biomass, especially the lignin portions of the biomass.

With respect to thermal effects on inorganic materials in electronbeams, differential electron beam absorption (dE/dx) in matter isdescribed by equation (1):

dE/dx=−S(V)ρ (in MeV/cm)  (1),

where S(V) (MeV·cm²/g) is the stopping power of the material toelectrons at energy V, and ρ is the mass density of the material (ing/cm³).

Using the same parameters, the electron range (R), which is the maximumpenetration distance of electrons of energy V₀ into the material, isapproximated by equation (2):

R=V ₀ /S(V ₀)ρ (in cm)  (2).

Assuming no heat conduction, the temperature rise (ΔT in K) in amaterial being irradiated with energetic electrons is inverselyproportion to the specific heat capacity of the material (C_(p)),material density (ρ), unit area (a) and thickness (d), and directlyproportional to the deposited energy density (ε), as shown in equation(3):

ΔT=ε/C _(p) ρad (in K)  (3).

When heat conduction is considered, heat is conducted away from theheated region and equilibrates on a time scale (τ) that is inverselyproportional the thermal conductivity of the material. If energy is putinto the material on a time scale shorter than (τ), the material willrise in temperature. With a beam of electrons it is possible to locallyelevate temperatures of a material being irradiated up to 25,000° C. orgreater.

Examples of suitable inorganic materials are discussed below in theMATERIALS section.

In some implementations, the biomass material is first physicallyprepared for processing, often by size reduction of a raw feedstock. Insome cases, the biomass material and/or the combination is treated withone or more additional processing steps such as sonication, oxidation,pyrolysis, or steam explosion.

The irradiated combination of biomass and inorganic material can be usedas a product in itself, or can be further processed to form one or moreproducts and in some cases co-products, as will be discussed below. Theinorganic material may be removed before, during or after furtherprocessing, or may remain in the final product(s).

Systems for Treating Biomass

FIG. 1 shows a system 100 for converting biomass, particularly biomasswith significant cellulosic and lignocellulosic components and/orstarchy components, into useful products and co-products. System 100includes a feed preparation subsystem 110, a combining unit 113, atreatment subsystem 114, a primary process subsystem 118, and apost-processing subsystem 122. Feed preparation subsystem 110 receivesbiomass in its raw form, physically prepares the biomass for use asfeedstock by downstream processes (e.g., reduces the size of andhomogenizes the biomass), and stores the biomass both in its raw andfeedstock forms. In the combining unit 113, the biomass is combined withan inorganic material, which is generally in particulate form.

Treatment subsystem 114 receives the combination from the combining unit113, and prepares the feedstock for use in a primary production processsuch as fermentation by, for example, reducing the average molecularweight and crystallinity of the feedstock. In the treatment subsystem114, the combination is irradiated, and may also be subjected to othertreatments, such as quenching, pyrolysis, or oxidation.

Primary process subsystem 118 receives the treated feedstock frompretreatment subsystem 114 and uses it as a feedstock to produce usefulproducts (e.g., ethanol, other alcohols, pharmaceuticals, and/or foodproducts).

The feed preparation system, combining unit, treatment subsystem, andprimary process subsystem 118 may be in the same production facility, ormay be in two or more production facilities. For example, the biomassmaterial can be physically prepared at a first facility, combined withthe inorganic material and irradiated at a second facility, andprocessed in a primary process at the second facility or a thirdfacility.

In some cases, the output of primary process subsystem 118 is directlyuseful but, in other cases, all or a portion of the output may requirefurther processing, e.g., distillation, provided by post-processingsubsystem 122. Post-processing subsystem 122 can also provide treatmentfor waste streams from the other subsystems. In some cases, theco-products of subsystems 114, 118, 122 can also be directly orindirectly useful as secondary products and/or in increasing the overallefficiency of system 100. For example, post-processing subsystem 122 canproduce treated water to be recycled for use as process water in othersubsystems and/or can produce burnable waste which can be used as fuelfor boilers producing steam and/or electricity.

The inorganic material may in some cases be separated from the treatedfeedstock by a separation unit 120. Separation unit 120 may be beforethe primary process subsystem 118, as shown, or may be after the primaryprocess subsystem or post-processing subsystem, or integrated witheither of these subsystems. In some cases the inorganic material isrecovered, e.g., to be re-used in the process or used as a co-product.In other cases the inorganic material is discarded. In someimplementations the inorganic material is not separated from the biomassbut instead becomes part of the final product.

Biomass Feedstock Preparation

In some cases, feed preparation system 110 prepares the feedstock bycutting, grinding, shearing, shredding, mechanical ripping or tearing,pin grinding, air attrition milling, or chopping. If desired, screensand/or magnets can be used to remove oversized or undesirable objectssuch as, for example, rocks or nails from the feed stream. Such physicalpreparation, e.g., by shearing, can be “open up” and stress the fibrousmaterials, making the cellulose of the materials more susceptible tochain scission and/or reduction of crystallinity. The open materials canalso be more susceptible to oxidation when irradiated. Physicalpreparation can also make it easier to combine the biomass material withthe inorganic material, for example by reducing the size of the biomassmaterial and rendering it more homogeneous in size and shape.

In the example shown in FIG. 2, a biomass fiber source 210 is sheared,e.g., in a rotary knife cutter, to provide a first fibrous material 212.The first fibrous material 212 is passed through a first screen 214having an average opening size of 1.59 mm or less ( 1/16 inch, 0.0625inch) to provide a second fibrous material 216. If desired, the biomassfiber source can be cut prior to shearing, e.g., with a shredder, forexample, a counter-rotating screw shredder, such as those manufacturedby Munson (Utica, N.Y.), or with a guillotine cutter.

In some implementations, a rotary knife cutter is used to concurrentlyshear the fiber source and screen the first fibrous material. Referringto FIG. 3, a rotary knife cutter 220 includes a hopper 222 that can beloaded with a shredded fiber source 224 prepared by shredding fibersource. Shredded fiber source is sheared between stationary blades 230and rotating blades 232 to provide a first fibrous material 240. Firstfibrous material 240 passes through screen 242, and the resulting secondfibrous material 244 is captured in bin 250. To aid in the collection ofthe second fibrous material, the bin can have a pressure below nominalatmospheric pressure, e.g., at least 10 percent below nominalatmospheric pressure, e.g., at least 25 percent below nominalatmospheric pressure, at least 50 percent below nominal atmosphericpressure, or at least 75 percent below nominal atmospheric pressure. Insome embodiments, a vacuum source 252 is utilized to maintain the binbelow nominal atmospheric pressure. Suitable characteristics of thescreen are described, for example, in U.S. Ser. No. 12/429,045.

The fiber source can be sheared in a dry state, a hydrated state (e.g.,having up to ten percent by weight absorbed water), or in a wet state,e.g., having between about 10 percent and about 75 percent by weightwater. The fiber source can even be sheared while partially or fullysubmerged under a liquid, such as water, ethanol, isopropanol. The fibersource can also be sheared in under a gas (such as a stream oratmosphere of gas other than air), e.g., oxygen or nitrogen, or steam.

If desired, the fibrous materials can be separated, e.g., continuouslyor in batches, into fractions according to their length, width, density,material type, or some combination of these attributes. For example, forforming composites, it is often desirable to have a relatively narrowdistribution of fiber lengths.

The fibrous materials can irradiated immediately following theirpreparation, or they can may be dried, e.g., at approximately 105° C.for 4-18 hours, so that the moisture content is, e.g., less than about0.5% before use.

In some embodiments, the second fibrous material is sheared and passedthrough the first screen, or a different sized screen. In someembodiments, the second fibrous material is passed through a secondscreen having an average opening size equal to or less than that offirst screen. Referring to FIG. 4, a third fibrous material 220 can beprepared from the second fibrous material 216 by shearing the secondfibrous material 216 and passing the resulting material through a secondscreen 222 having an average opening size less than the first screen214. The sequence of shearing and screening can be repeated as manytimes as desired to obtain particular fiber properties.

Generally, the fibers of the fibrous materials can have a relativelylarge average length-to-diameter ratio (e.g., greater than 20-to-1),even if they have been sheared more than once. In addition, the fibersof the fibrous materials described herein may have a relatively narrowlength and/or length-to-diameter ratio distribution.

As used herein, average fiber widths (i.e., diameters) are thosedetermined optically by randomly selecting approximately 5,000 fibers.Average fiber lengths are corrected length-weighted lengths. BET(Brunauer, Emmet and Teller) surface areas are multi-point surfaceareas, and porosities are those determined by mercury porosimetry.

The average length-to-diameter ratio of the second fibrous material 14can be, e.g., greater than 8/1, e.g., greater than 10/1, greater than15/1, greater than 20/1, greater than 25/1, or greater than 50/1. Anaverage length of the second fibrous material 14 can be, e.g., betweenabout 0.5 mm and 2.5 mm, e.g., between about 0.75 mm and 1.0 mm, and anaverage width (i.e., diameter) of the second fibrous material 14 can be,e.g., between about 5 μm and 50 μm, e.g., between about 10 μm and 30 μm.

In some embodiments, a standard deviation of the length of the secondfibrous material 14 is less than 60 percent of an average length of thesecond fibrous material 14, e.g., less than 50 percent of the averagelength, less than 40 percent of the average length, less than 25 percentof the average length, less than 10 percent of the average length, lessthan 5 percent of the average length, or even less than 1 percent of theaverage length.

In some embodiments, the material has a bulk density of less than 0.25g/cm³, e.g., 0.20 g/cm³, 0.15 g/cm³, 0.10 g/cm³, 0.05 g/cm³ or less,e.g., 0.025 g/cm³. Bulk density is determined using ASTM D1895B.Briefly, the method involves filling a measuring cylinder of knownvolume with a sample and obtaining a weight of the sample. The bulkdensity is calculated by dividing the weight of the sample in grams bythe known volume of the cylinder in cubic centimeters.

In some embodiments, a BET surface area of the second fibrous materialis greater than 0.1 m²/g, e.g., greater than 0.25 m²/g, greater than 0.5m²/g, greater than 1.0 m²/g, greater than 1.5 m²/g, greater than 1.75m²/g, greater than 5.0 m²/g, greater than 10 m²/g, greater than 25 m²/g,greater than 35 m²/g, greater than 50 m²/g, greater than 60 m²/g,greater than 75 m²/g, greater than 100 m²/g, greater than 150 m²/g,greater than 200 m²/g, or even greater than 250 m²/g. A porosity of thesecond fibrous material 14 can be, e.g., greater than 20 percent,greater than 25 percent, greater than 35 percent, greater than 50percent, greater than 60 percent, greater than 70 percent, e.g., greaterthan 80 percent, greater than 85 percent, greater than 90 percent,greater than 92 percent, greater than 94 percent, greater than 95percent, greater than 97.5 percent, greater than 99 percent, or evengreater than 99.5 percent.

In some embodiments, a ratio of the average length-to-diameter ratio ofthe first fibrous material to the average length-to-diameter ratio ofthe second fibrous material is, e.g., less than 1.5, e.g., less than1.4, less than 1.25, less than 1.1, less than 1.075, less than 1.05,less than 1.025, or even substantially equal to 1.

Any fibrous material described herein, or any mixture of fibrousmaterial with an inorganic material, can be densified before or afterirradiation, e.g., for transport or storage, and then “opened up” forfurther processing by any one or more methods described herein.Densification is described, for example, in U.S. Ser. No. 12/429,045.

Combination of the Biomass Material with the Inorganic Material

In some embodiments, the cellulosic and/or lignocellulosic material andinorganic material are combined by dry blending, such as in a drum priorto irradiating. In other embodiments, the cellulosic and/orlignocellulosic material and the inorganic material are co-comminuted.For example, the cellulosic and/or lignocellulosic material andinorganic material can be ground together in a mill prior to irradiationof the mixture. In particular embodiments, the cellulosic and/orlignocellulosic material and inorganic material are co-comminuted in afreezer mill such that each material is cooled to a temperature below25° C., such as at or below 0° C., such as at or below the normalatmospheric sublimation temperature of dry ice, or at or below thenormal atmospheric boiling point of liquid nitrogen. Grinding biomass ina freezer mill is described in U.S. Provisional Patent Application Ser.No. 61/081,709, entitled “Cooling and Processing Materials,” which isincorporated herein by reference in its entirety.

Treatment

Treatment includes irradiating the combination of the physicallyprepared biomass material and the inorganic material. In some cases,treatment can further include one or more of sonication, oxidation,pyrolysis, and steam explosion, any of which can be modulated, e.g.,enhanced, by the use of inorganic additives as described herein.

Radiation Treatment

Irradiating the combination can include subjecting the combination toaccelerated electrons, such as electrons having an energy of greaterthan about 2 MeV, 4 MeV, 6 MeV, or even greater than about 8 MeV. Thus,ranges, such as ranges of 2.0 to 8.0 MeV and 4.0 to 6.0 MeV, arecontemplated. In some embodiments, electrons are accelerated to, forexample, a speed of greater than 75 percent of the speed of light, e.g.,greater than 85, 90, 95, or 99 percent of the speed of light.

In some instances, the irradiation is performed at a dosage rate ofgreater than about 0.25 Mrad per second, e.g., greater than about 0.5,0.75, 1.0, 1.5, 2.0, or even greater than about 2.5 Mrad per second. Insome embodiments, the irradiating is performed at a dose rate of between5.0 and 1500.0 kilorads/hour, e.g., between 10.0 and 750.0 kilorads/houror between 50.0 and 350.0 kilorads/hours.

In some embodiments, the irradiating (with any radiation source or acombination of sources) is performed until the material receives a doseof at least 0.25 Mrad, e.g., at least 1.0 Mrad, at least 2.5 Mrad, atleast 5.0 Mrad, or at least 10.0 Mrad. In some embodiments, theirradiating is performed until the material receives a dose of between1.0 Mrad and 6.0 Mrad, e.g., between 1.5 Mrad and 4.0 Mrad.

The dose applied will depend on the desired effect and the particularfeedstock. For example, high doses of radiation can break chemical bondswithin feedstock components and low doses of radiation can increasechemical bonding (e.g., cross-linking) within feedstock components.

Radiation can be applied to any sample that is dry or wet, or evendispersed in a liquid, such as water. For example, irradiation can beperformed on cellulosic and/or lignocellulosic material in which lessthan about 25 percent by weight of the cellulosic and/or lignocellulosicmaterial has surfaces wetted with a liquid, such as water. In someembodiments, irradiating is performed on cellulosic and/orlignocellulosic material in which substantially none of the cellulosicand/or lignocellulosic material is wetted with a liquid, such as water.

In some embodiments, any processing described herein occurs after thecellulosic and/or lignocellulosic material remains dry as acquired orhas been dried, e.g., using heat and/or reduced pressure. For example,in some embodiments, the cellulosic and/or lignocellulosic material hasless than about five percent by weight retained water, measured at 25°C. and at fifty percent relative humidity.

Radiation can be applied while the cellulosic and/or lignocellulosic isexposed to air, oxygen-enriched air, or even oxygen itself, or blanketedby an inert gas such as nitrogen, argon, or helium. When maximumoxidation is desired, an oxidizing environment is utilized, such as airor oxygen and the distance from the radiation source is optimized tomaximize reactive gas formation, e.g., ozone and/or oxides of nitrogen.

Radiation may be applied under a pressure of greater than about 2.5atmospheres, such as greater than 5, 10, 15, 20, or even greater thanabout 50 atmospheres.

Irradiating can be performed utilizing an ionizing radiation, such asgamma rays, x-rays, energetic ultraviolet radiation, such as ultravioletC radiation having a wavelength of from about 100 nm to about 280 nm, abeam of particles, such as a beam of electrons, slow neutrons or alphaparticles. In some embodiments, irradiating includes two or moreradiation sources, such as gamma rays and a beam of electrons, which canbe applied in either order or concurrently.

In some embodiments, energy deposited in a material that releases anelectron from its atomic orbital is used to irradiate the materials. Theradiation may be provided by 1) heavy charged particles, such as alphaparticles or protons, 2) electrons, produced, for example, in beta decayor electron beam accelerators, or 3) electromagnetic radiation, forexample, gamma rays, x rays, or ultraviolet rays. In one approach,radiation produced by radioactive substances can be used to irradiatethe feedstock. In some embodiments, any combination in any order orconcurrently of (1) through (3) may be utilized.

In some instances when chain scission is desirable and/or polymer chainfunctionalization is desirable, particles heavier than electrons, suchas protons, helium nuclei, argon ions, silicon ions, neon ions, carbonions, phosphorus ions, oxygen ions or nitrogen ions can be utilized.When ring-opening chain scission is desired, positively chargedparticles can be utilized for their Lewis acid properties for enhancedring-opening chain scission.

In some embodiments, the irradiated biomass has a number averagemolecular weight (M_(N2)) that is lower than the number averagemolecular weight of the biomass prior to irradiation (^(T)M_(N1)) bymore than about 10 percent, e.g., 15, 20, 25, 30, 35, 40, 50 percent, 60percent, or even more than about 75 percent.

In some embodiments, the starting number average molecular weight (priorto irradiation) is from about 200,000 to about 3,200,000, e.g., fromabout 250,000 to about 1,000,000 or from about 250,000 to about 700,000,and the number average molecular weight after irradiation is from about50,000 to about 200,000, e.g., from about 60,000 to about 150,000 orfrom about 70,000 to about 125,000. However, in some embodiments, e.g.,after extensive irradiation, it is possible to have a number averagemolecular weight of less than about 10,000 or even less than about5,000.

In some instances, the irradiated biomass has cellulose that has ascrystallinity (^(T)C₂) that is lower than the crystallinity (^(T)C₁) ofthe cellulose of the biomass prior to irradiation. For example, (^(T)C₂)can be lower than (^(T)C₁) by more than about 10 percent, e.g., 15, 20,25, 30, 35, 40, or even more than about 50 percent.

In some embodiments, the starting crystallinity index (prior toirradiation) is from about 40 to about 87.5 percent, e.g., from about 50to about 75 percent or from about 60 to about 70 percent, and thecrystallinity index after irradiation is from about 10 to about 50percent, e.g., from about 15 to about 45 percent or from about 20 toabout 40 percent. However, in some embodiments, e.g., after extensiveirradiation, it is possible to have a crystallinity index of lower than5 percent. In some embodiments, the material after irradiation issubstantially amorphous.

In some embodiments, the irradiated biomass can have a level ofoxidation (^(T)O₂) that is higher than the level of oxidation (^(T)O₁)of the biomass prior to irradiation. A higher level of oxidation of thematerial can aid in its dispersability, swellability and/or solubility,further enhancing the materials susceptibility to chemical, enzymatic orbiological attack. The irradiated biomass material can also have morehydroxyl groups, aldehyde groups, ketone groups, ester groups orcarboxylic acid groups, which can increase its hydrophilicity.

Ionizing Radiation

Each form of radiation ionizes the biomass via particular interactions,as determined by the energy of the radiation. Heavy charged particlesprimarily ionize matter via Coulomb scattering; furthermore, theseinteractions produce energetic electrons that may further ionize matter.Alpha particles are identical to the nucleus of a helium atom and areproduced by the alpha decay of various radioactive nuclei, such asisotopes of bismuth, polonium, astatine, radon, francium, radium,several actinides, such as actinium, thorium, uranium, neptunium,curium, californium, americium, and plutonium.

When particles are utilized, they can be neutral (uncharged), positivelycharged or negatively charged. When charged, the charged particles canbear a single positive or negative charge, or multiple charges, e.g.,one, two, three or even four or more charges. In instances in whichchain scission is desired, positively charged particles may bedesirable, in part, due to their acidic nature. When particles areutilized, the particles can have the mass of a resting electron, orgreater, e.g., 500, 1000, 1500, or 2000 or more, e.g., 10,000 or even100,000 times the mass of a resting electron. For example, the particlescan have a mass of from about 1 atomic unit to about 150 atomic units,e.g., from about 1 atomic unit to about 50 atomic units, or from about 1to about 25, e.g., 1, 2, 3, 4, 5, 10, 12 or 15 amu. Accelerators used toaccelerate the particles can be electrostatic DC, electrodynamic DC, RFlinear, magnetic induction linear, or continuous wave. For example,cyclotron type accelerators are available from IBA, Belgium, such as theRhodatron® system, while DC type accelerators are available from RDI,now IBA Industrial, such as the Dynamitron®. Exemplary ions and ionaccelerators are discussed in Introductory Nuclear Physics, Kenneth S.Krane, John Wiley & Sons, Inc. (1988), Krsto Prelec, FIZIKA B 6 (1997)4, 177-206, Chu, William T., “Overview of Light-Ion Beam Therapy”,Columbus-Ohio, ICRU-IAEA Meeting, 18-20 Mar. 2006, Iwata, Y. et al.,“Alternating-Phase-Focused IH-DTL for Heavy-Ion Medical Accelerators”,Proceedings of EPAC 2006, Edinburgh, Scotland, and Leitner, C. M. etal., “Status of the Superconducting ECR Ion Source Venus”, Proceedingsof EPAC 2000, Vienna, Austria.

Electrons interact via Coulomb scattering and bremsstrahlung radiationproduced by changes in the velocity of electrons. Electrons may beproduced by radioactive nuclei that undergo beta decay, such as isotopesof iodine, cesium, technetium, and iridium. Alternatively, an electrongun can be used as an electron source via thermionic emission.

Electromagnetic radiation interacts via three processes: photoelectricabsorption, Compton scattering, and pair production. The dominatinginteraction is determined by the energy of the incident radiation andthe atomic number of the material. The summation of interactionscontributing to the absorbed radiation in cellulosic material can beexpressed by the mass absorption coefficient (see “Ionization Radiation”in PCT/US2007/022719).

Electromagnetic radiation can be subclassified as gamma rays, x rays,ultraviolet rays, infrared rays, microwaves, or radiowaves, depending onwavelength.

Gamma radiation has the advantage of a significant penetration depthinto a variety of material in the sample. Sources of gamma rays includeradioactive nuclei, such as isotopes of cobalt, calcium, technicium,chromium, gallium, indium, iodine, iron, krypton, samarium, selenium,sodium, thallium, and xenon.

Sources of x rays include electron beam collision with metal targets,such as tungsten or molybdenum or alloys, or compact light sources, suchas those produced commercially by Lyncean.

Sources for ultraviolet radiation include deuterium or cadmium lamps.

Sources for infrared radiation include sapphire, zinc, or selenidewindow ceramic lamps.

Sources for microwaves include klystrons, Slevin type RF sources, oratom beam sources that employ hydrogen, oxygen, or nitrogen gases.

Electron Beam

In some embodiments, a beam of electrons is used as the radiationsource. A beam of electrons has the advantages of high dose rates (e.g.,1, 5, or even 10 Mrad per second), high throughput, less containment,and less confinement equipment. Electrons can also be more efficient atcausing chain scission. In addition, electrons having energies of 4-10MeV can have a penetration depth of 5 to 30 mm or more, such as 40 mm.

Electron beams can be generated, e.g., by electrostatic generators,cascade generators, transformer generators, low energy accelerators witha scanning system, low energy accelerators with a linear cathode, linearaccelerators, and pulsed accelerators. Electrons as an ionizingradiation source can be useful, e.g., for relatively thin piles ofmaterials, e.g., less than 0.5 inch, e.g., less than 0.4 inch, 0.3 inch,0.2 inch, or less than 0.1 inch. In some embodiments, the energy of eachelectron of the electron beam is from about 0.3 MeV to about 2.0 MeV(million electron volts), e.g., from about 0.5 MeV to about 1.5 MeV, orfrom about 0.7 MeV to about 1.25 MeV.

In some embodiments, electrons used to treat biomass material can haveaverage energies of 0.05 c or more (e.g., 0.10 c or more, 0.2 c or more,0.3 c or more, 0.4 c or more, 0.5 c or more, 0.6 c or more, 0.7 c ormore, 0.8 c or more, 0.9 c or more, 0.99 c or more, 0.9999 c or more),where c corresponds to the vacuum velocity of light.

Electron beam irradiation devices may be procured commercially from IonBeam Applications, Louvain-la-Neuve, Belgium or the Titan Corporation,San Diego, Calif. Typical electron energies can be 1 MeV, 2 MeV, 4.5MeV, 7.5 MeV, or 10 MeV. Typical electron beam irradiation device powercan be 1 kW, 5 kW, 10 kW, 20 kW, 50 kW, 100 kW, 250 kW, or 500 kW.Effectiveness of depolymerization of the feedstock slurry depends on theelectron energy used and the dose applied, while exposure time dependson the power and dose. Typical doses may take values of 1 kGy, 5 kGy, 10kGy, 20 kGy, 50 kGy, 100 kGy, or 200 kGy.

Tradeoffs in considering electron beam irradiation device powerspecifications include cost to operate, capital costs, depreciation, anddevice footprint. Tradeoffs in considering exposure dose levels ofelectron beam irradiation would be energy costs and environment, safety,and health (ESH) concerns. Tradeoffs in considering electron energiesinclude energy costs; here, a lower electron energy may be advantageousin encouraging depolymerization of certain feedstock slurry (see, forexample, Bouchard, et al, Cellulose (2006) 13: 601-610).

It may be advantageous to provide a double-pass of electron beamirradiation in order to provide a more effective depolymerizationprocess. For example, the feedstock transport device could direct thefeedstock (in dry or slurry form) underneath and in a reverse directionto its initial transport direction. Double-pass systems can allowthicker feedstock slurries to be processed and can provide a moreuniform depolymerization through the thickness of the feedstock slurry.

The electron beam irradiation device can produce either a fixed beam ora scanning beam. A scanning beam may be advantageous with large scansweep length and high scan speeds, as this would effectively replace alarge, fixed beam width. Further, available sweep widths of 0.5 m, 1 m,2 m or more are available.

Ion Particle Beams

Particles heavier than electrons can be utilized to irradiatecarbohydrates or materials that include carbohydrates, e.g., cellulosicmaterials, lignocellulosic materials, starchy materials, or mixtures ofany of these and others described herein. For example, protons, heliumnuclei, argon ions, silicon ions, neon ions carbon ions, phosphorusions, oxygen ions or nitrogen ions can be utilized. In some embodiments,particles heavier than electrons can induce higher amounts of chainscission. In some instances, positively charged particles can inducehigher amounts of chain scission than negatively charged particles dueto their acidity.

Heavier particle beams can be generated, e.g., using linear acceleratorsor cyclotrons. In some embodiments, the energy of each particle of thebeam is from about 1.0 MeV/atomic unit to about 6,000 MeV/atomic unit,e.g., from about 3 MeV/atomic unit to about 4,800 MeV/atomic unit, orfrom about 10 MeV/atomic unit to about 1,000 MeV/atomic unit.

Ion beam treatment is discussed in detail in U.S. Ser. No. 12/417,699.

Electromagnetic Radiation

In embodiments in which the irradiating is performed withelectromagnetic radiation, the electromagnetic radiation can have, e.g.,energy per photon (in electron volts) of greater than 10² eV, e.g.,greater than 10³, 10⁴, 10⁵, 10⁶, or even greater than 10⁷ eV. In someembodiments, the electromagnetic radiation has energy per photon ofbetween 10⁴ and 10⁷, e.g., between 10⁵ and 10⁶ eV. The electromagneticradiation can have a frequency of, e.g., greater than 10¹⁶ hz, greaterthan 10¹⁷ hz, 10¹⁸, 10¹⁹, 10²⁰, or even greater than 10²¹ hz. In someembodiments, the electromagnetic radiation has a frequency of between10¹⁸ and 10²² hz, e.g., between 10¹⁹ to 10²¹ hz.

Combinations of Radiation Treatments

In some embodiments, two or more radiation sources are used, such as twoor more ionizing radiations. For example, samples can be treated, in anyorder, with a beam of electrons, followed by gamma radiation and UVlight having wavelengths from about 100 nm to about 280 nm. In someembodiments, samples are treated with three ionizing radiation sources,such as a beam of electrons, gamma radiation, and energetic UV light.

Quenching and Controlled Functionalization of Biomass

After treatment with one or more ionizing radiations, such as photonicradiation (e.g., X-rays or gamma-rays), e-beam radiation or particlesheavier than electrons that are positively or negatively charged (e.g.,protons or carbon ions), any of the mixtures of carbohydrate-containingmaterials and inorganic materials described herein become ionized; thatis, they include radicals at levels that are detectable with an electronspin resonance spectrometer. The current practical limit of detection ofthe radicals is about 10¹⁴ spins at room temperature. After ionization,any biomass material that has been ionized can be quenched to reduce thelevel of radicals in the ionized biomass, e.g., such that the radicalsare no longer detectable with the electron spin resonance spectrometer.For example, the radicals can be quenched by the application of asufficient pressure to the biomass and/or by utilizing a fluid incontact with the ionized biomass, such as a gas or liquid, that reactswith (quenches) the radicals. The use of a gas or liquid to at least aidin the quenching of the radicals also allows the operator to controlfunctionalization of the ionized biomass with a desired amount and kindof functional groups, such as carboxylic acid groups, enol groups,aldehyde groups, nitro groups, nitrile groups, amino groups, alkyl aminogroups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups. Insome instances, such quenching can improve the stability of some of theionized biomass materials. For example, quenching can improve theresistance of the biomass to oxidation. Functionalization by quenchingcan also improve the solubility of any biomass described herein, canimprove its thermal stability, which can be important in the manufactureof composites, and can improve material utilization by variousmicroorganisms. For example, the functional groups imparted to thebiomass material by quenching can act as receptor sites for attachmentby microorganisms, e.g., to enhance cellulose hydrolysis by variousmicroorganisms.

If the ionized biomass remains in the atmosphere, it will be oxidized,such as to an extent that carboxylic acid groups are generated byreaction with the atmospheric oxygen. In some instances with somematerials, such oxidation is desired because it can aid in the furtherbreakdown in molecular weight of the carbohydrate-containing biomass,and the oxidation groups, e.g., carboxylic acid groups can be helpfulfor solubility and microorganism utilization in some instances. However,since the radicals can “live” for some time after irradiation, e.g.,longer than 1 day, 5 days, 30 days, 3 months, 6 months or even longerthan 1 year, material properties can continue to change over time, whichin some instances, can be undesirable.

Detecting radicals in irradiated samples by electron spin resonancespectroscopy and radical lifetimes in such samples is discussed inBartolotta et al., Physics in Medicine and Biology, 46 (2001), 461-471and in Bartolotta et al., Radiation Protection Dosimetry, Vol. 84, Nos.1-4, pp. 293-296 (1999), the contents of each of which are incorporatedherein by reference.

Sonication, Pyrolysis, Oxidation

One or more sonication, pyrolysis, and/or oxidative processing sequencescan be used to process raw feedstock from a wide variety of differentsources to extract useful substances from the feedstock, and to providepartially degraded organic material which functions as input to furtherprocessing steps and/or sequences. Such processing can reduce themolecular weight and/or crystallinity of feedstock and biomass, e.g.,one or more carbohydrate sources, such as cellulosic or lignocellulosicmaterials, or starchy materials. These processes are described in detailin U.S. Ser. No. 12/429,045.

Other Processes

Steam explosion can be used alone without any of the processes describedherein, or in combination with any of the processes described herein.

Any processing technique described herein can be used at pressure aboveor below normal, earth-bound atmospheric pressure. For example, anyprocess that utilizes radiation, sonication, oxidation, pyrolysis, steamexplosion, or combinations of any of these processes to providematerials that include a carbohydrate can be performed under highpressure, which can increase reaction rates. For example, any process orcombination of processes can be performed at a pressure greater thanabout greater than 25 MPa, e.g., greater than 50 MPa, 75 MPa, 100 MPa,150 MPa, 200 MPa, 250 MPa, 350 MPa, 500 MPa, 750 MPa, 1,000 MPa, orgreater than 1,500 MPa.

Primary Processes and Post-Processing

Materials treated using any of the processes described herein can thenbe subjected to other processes, for example primary processes such asfermentation and gasification, and/or post-processing steps such asdistillation, wastewater processing, waste combustion, and the like.Such processes are described in detail in the patent applications thathave been incorporated by reference herein, e.g., in 12/429,045.

Products/Co-Products

Using such primary processes and/or post-processing, the treated biomasscan be converted to one or more products, for example alcohols, e.g.,methanol, ethanol, propanol, isopropanol, butanol, e.g., n-, sec- ort-butanol, ethylene glycol, propylene glycol, 1,4-butane diol, glycerinor mixtures of these alcohols; organic acids, such as formic acid,acetic acid, propionic acid, butyric acid, valeric acid, caproic,palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid,glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid,γ-hydroxybutyric acid or mixtures of these acids; food products; animalfeed; pharmaceuticals; or nutriceuticals. Co-products that may beproduced include lignin residue.

Materials Inorganic Materials

In some embodiments, the inorganic material is or includes a metal or ametal alloy. For example, the metal can include a base metal, such asiron, nickel, lead, copper or zinc, a ferrous metal, such as wroughtiron or pig iron, a noble metal, such as tantalum, gold, platinum orrhodium, a precious metal, such as ruthenium, rhodium, palladium,osmium, iridium, or platinum, or a transition metal, e.g., elements 21to 30 (inclusive), 39 to 48 (inclusive), 71 to 80 (inclusive), and 103to 112 from the periodic table of elements.

In specific embodiments, the inorganic material is or includes a metalalloy, such a binary or ternary alloy. In particular embodiments, thealloy is or includes steel, brass, bronze, duralumin, hastaloy, Al—Lialloy, alnico alloy, nambe alloy, silumin alloy, AA-8000 and magnaliumalloy.

In one embodiment, the inorganic material is or includes aluminum, suchas waste packaging that includes an aluminum layer.

In other embodiments, the inorganic material is or includes a metalliccompound, such as inorganic compound of iron or cobalt, such as aninorganic iron or cobalt compound in which the iron or cobalt is in the2+ or 3+ oxidation state. Examples of such iron compounds are ammoniumiron(II) sulfate hexahydrate, ammonium iron(II) sulfate solution,ammonium iron(III) sulfate dodecahydrate, ammonium iron(III) sulfate,iron(II) sulfate heptahydrate, iron(II) sulfate hydrate, iron(II)sulfate solution, and iron(III) sulfate hydrate.

In still other embodiments, inorganic material is or includes arefractory material, such as an acidic, neutral or basic refractory.Examples of acidic refractory materials include zircon, fireclay andsilica. Examples of neutral refractory materials include alumina,chromite, silicon carbide, carbon and mulitite. Examples of basicrefractory materials include dolomite or magnesite.

In yet other embodiments, the inorganic material includes a ceramic,such as an oxide, a carbide, a boride, a nitride, a silicide, or akaolin (e.g., natural, neutral, acidic, basic, or whitened). Forexample, the oxide can be an aluminum oxide, such as alumina, azirconium oxide, a silicon oxide, a zinc oxide, or a titanium oxide,such as titanium dioxide.

In some embodiments, the inorganic additive includes between about 0.25and about 25 percent by weight water therein and/or thereon. In aspecific embodiment, the inorganic material includes water of hydrationthat is capable of leaving the inorganic material at elevatedtemperatures, such as hydrated alumina.

Other examples of useful inorganic materials include calcium carbonate,aragonite clay, orthorhombic clays, calcite clay, rhombohedral clays,bentonite clay, dicalcium phosphate, dicalcium phosphate anhydrous,dicalcium phosphate dihydrate, tricalcium phosphate, calciumpyrophosphate, insoluble sodium metaphosphate, precipitated calciumcarbonate, magnesium orthophosphate, trimagnesium phosphate,hydroxyapatites, synthetic apatites, hydrated silica xerogel, metalaluminosilicate complexes, sodium aluminum silicates, zirconiumsilicate, sand, glass, stone, rock, montmorillonite, and shale.

In some embodiments, the inorganic material has a melting point ofgreater than about 400° C., such as greater than about 500, 600, 700,800, 900, 1000, 1200, 1,400, 1600, 1800, 2000, 2200, 2400, 2600 or evengreater than 2800° C. In other instances, the inorganic material doesnot have or does not include a material having a melting point.

In some instances, the inorganic material has a specific heat capacityC_(p) of less than about 1.5 J/gK, such as less than about 1.25, 1.0,0.75, 0.50, 0.25 or even less than about 0.1 J/gK. In various examples,the inorganic material can have a specific heat capacity C_(p) ofbetween about 1.25 and about 0.2 J/gK, such between about 1.15 and about0.25 or between about 0.85 and 0.30 J/gK.

The inorganic material can have a thermal conductivity of between about0.004 and about 450 W/mK, between about 0.04 and about 250 W/mK, betweenabout 0.1 and about 150 W/mK, or between about 0.25 and about 50 W/mK.

The inorganic material can have a density of greater than about 1.5g/cm³, such as greater than about 2.0, 2.5, 3.0, 5.0, 7.0, 8.0, 9.0,12.0, 15.0, 18.0, or even greater than 20.0 g/cm³. The inorganicmaterial can have a density of between about greater 3.5 g/cm³ and about20.0 g/cm³, between about 4.0 g/cm³ and about 18 g/cm³ or between about4.5 g/cm³ and about 13 g/cm³.

In some instances, the inorganic material is or includes particles whichare substantially spherical in shape, and that have an average particlesize, e.g., diameter, that ranges from about 0.1 micron to about 100microns, from about 0.25 micron to about 75 microns or from about 0.5micron to about 50 microns. In some cases, the particle size can rangefrom about 10 mm to about 1000 mm. The particles may also be in the formof fibers, plates, or have other morphologies. The particles may have asurface area of, for example, about 0.5 to 500 m²/g.

To maximize the effect of the inorganic additive, the combination canhave between about 0.05 to about 35 percent by weight inorganicmaterial, such as between about 0.1 to about 20 percent by weightinorganic material or between about 0.5 and about 10 percent by weightof the inorganic material.

Biomass Materials

Generally, any biomass material that is or includes a carbohydrate,composed entirely of one or more saccharide units or that include one ormore saccharide units, can be processed by any of the methods describedherein. For example, the biomass material can be cellulosic,lignocellulosic, starch, or sugars.

For example, such materials can include fibrous materials such as paper,paper products, wood, wood-related materials, particle board, grasses,rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, sisal, abaca,straw, corn cobs, rice hulls, coconut hair, algae, seaweed, cotton,synthetic celluloses, or mixtures of any of these.

In some cases the biomass is a microbial material. Microbial sourcesinclude, but are not limited to, any naturally occurring or geneticallymodified microorganism or organism that contains or is capable ofproviding a source of carbohydrates (e.g., cellulose), for example,protists (e.g., animal (e.g., protozoa such as flagellates, amoeboids,ciliates, and sporozoa) and plant (e.g., algae such alveolates,chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes,red algae, stramenopiles, and viridaeplantae)), seaweed, plankton (e.g.,macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton,and femptoplankton), phytoplankton, bacteria (e.g., gram positivebacteria, gram negative bacteria, and extremophiles), yeast and/ormixtures of these. In some instances, microbial biomass can be obtainedfrom natural sources, e.g., the ocean, lakes, bodies of water, e.g.,salt water or fresh water, or on land. Alternatively or in addition,microbial biomass can be obtained from culture systems, e.g., largescale dry and wet culture systems.

Other biomass materials are discussed in the U.S. patent applicationsincorporated by reference hereinabove.

Other Embodiments Low Dose Irradiation and Composites

While irradiation has been discussed above primarily in the context ofreducing molecular weight and crystallinity of the biomass, in someembodiments, relatively low doses of radiation can crosslink, graft, orotherwise increase the molecular weight of a carbohydrate-containingmaterial. Such a material having increased molecular weight can beuseful, e.g., in making a composite having improved mechanicalproperties, such as abrasion resistance, compression strength, fractureresistance, impact strength, bending strength, tensile modulus, flexuralmodulus and elongation at break. Such a material having increasedmolecular weight can be useful in making a composition. Formingcomposites is described in WO 2006/102543, and in U.S. Ser. Nos.12/417,720 and 12/429,045.

Alternatively, a material, e.g., a fibrous material that includes afirst cellulosic and/or lignocellulosic material having a firstmolecular weight, in a mixture with an inorganic material, can becombined with a resin to provide a composite, and then the composite canbe irradiated with a relatively low dose of radiation so as to provide asecond cellulosic and/or lignocellulosic material having a secondmolecular weight higher than the first molecular weight. For example, ifgamma radiation is utilized as the radiation source, a dose of fromabout 1 Mrad to about 10 Mrad can be applied. Using this approachincreases the molecular weight of the material while it is within aresin matrix. In some embodiments, the resin is a cross-linkable resinand as such it crosslinks as the carbohydrate-containing materialincreases in molecular weight, which can provide a synergistic effect toprovide advantageous mechanical properties to the composite.

Treatment of Hydrocarbon-Containing Materials

In some embodiments, the methods and systems disclosed herein can beused to process hydrocarbon-containing materials such as tar or oilsands, oil shale, crude oil (e.g., heavy crude oil and/or light crudeoil), bitumen, coal, e.g., peat, lignite, sub-bituminous, bituminous andanthracite coal, petroleum gases (e.g., methane, ethane, propane,butane, isobutane), liquefied natural and/or synthetic gas, asphalt, andother natural materials that include various types of hydrocarbons. Forexample, a processing facility for hydrocarbon-containing materialsreceives a supply of raw material. The raw material can be delivereddirectly from a mine, e.g., by conveyor belt and/or rail car system, andin certain embodiments, the processing facility can be constructed inrelatively close proximity to, or even atop, the mine. In someembodiments, the raw material can be transported to the processingfacility via railway freight car or another motorized transport system,and/or pumped to the processing facility via pipeline.

When the raw material enters the processing facility, the raw materialcan be broken down mechanically and/or chemically to yield startingmaterial. As an example, the raw material can include material derivedfrom oil sands and containing crude bitumen. Bitumen can then beprocessed into one or more hydrocarbon products using the methodsdisclosed herein, for example by mixing the bitumen with an inorganicmaterial as described herein and irradiating the mixture. In someembodiments, the oil sands material can be extracted from surface minessuch as open pit mines. In certain embodiments, sub-surface oil sandsmaterial can be extracted using a hot water flotation process thatremoves oil from sand particles, and then adding naphtha to allowpumping of the oil to the processing facility.

For example, to process bitumen from oil sands, one or more of thetechniques disclosed herein can be used prior to any mechanicalbreakdown steps, following one or more mechanical breakdown steps, priorto cracking, after cracking and/or prior to hydrotreatment, and afterhydrotreatment. As another example, to process oil shale, one or more ofthe techniques disclosed herein can be used prior to either or both ofthe vaporization and purification steps discussed above. Productsderived from the hydrocarbon-based raw materials can be treated againwith any combination of techniques prior to transporting the productsout of the processing facility (e.g., either via motorized transport, orvia pipeline).

The techniques disclosed herein can be applied to process raw and/orintermediate material in dry form, in a solution or slurry, or ingaseous form (e.g., to process hydrocarbon vapors at elevatedtemperature). The solubility of raw or intermediate products insolutions and slurries can be controlled through selective addition ofone or more agents such as acids, bases, oxidizing agents, reducingagents, and salts. In general, the methods disclosed herein can be usedto initiate and/or sustain the reaction of raw and/or intermediatehydrocarbon-containing materials, extraction of intermediate materialsfrom raw materials (e.g., extraction of hydrocarbon components fromother solid or liquid components), distribution of raw and/orintermediate materials, and separation of intermediate materials fromraw materials (e.g., separation of hydrocarbon-containing componentsfrom other solid matrix components to increase the concentration and/orpurity and/or homogeneity of the hydrocarbon components).

In addition, microorganisms can be used for processing raw orintermediate materials, either prior to or following irradiation.Suitable microorganisms include various types of bacteria, yeasts, andmixtures thereof, as disclosed previously. The processing facility canbe equipped to remove harmful byproducts that result from the processingof raw or intermediate materials, including gaseous products that areharmful to human operators, and chemical byproducts that are harmful tohumans and/or various microorganisms.

In some embodiments, the use of one or more of the techniques disclosedherein results in a molecular weight reduction of one or more componentsof the raw or intermediate material that is processed. As a result,various lower weight hydrocarbon substances can be produced from one ormore higher weight hydrocarbon substances. In certain embodiments, theuse of one or more of the techniques disclosed herein results in anincrease in molecular weight of one or more components of the raw orintermediate material that is processed. For example, the varioustechniques disclosed herein can induce bond-formation between moleculesof the components, leading to the formation of increased quantities ofcertain products, and even to new, larger weight products. In additionto hydrocarbon products, various other compounds can be extracted fromthe raw materials, including nitrogen based compounds (e.g., ammonia),sulfur-based compounds, and silicates and other silicon-based compounds.In certain embodiments, one or more products extracted from the rawmaterials can be combusted to generate process heat for heating water,raw or intermediate materials, generating electrical power, or for otherapplications.

In some embodiments, processing raw and/or intermediate materials bymixing with an inorganic material and irradiating the mixture can leadto improvements in the efficiency (and even the elimination) of otherprocessing steps. For example, processing oil sand materials (includingbitumen) using one or more of the techniques disclosed herein can leadto more efficient cracking and/or hydrotreatment of the bitumen. Asanother example, processing oil shale can lead to more efficientextraction of various products, including shale oil and/or shale gas,from the oil shale. In certain embodiments, steps such as cracking orvaporization may not even be necessary if the techniques disclosedherein are first used to treat the raw material. Further, in someembodiments, by treating raw and/or intermediate materials, the productscan be made more soluble in certain solvents, in preparation forsubsequent processing steps in solution (e.g., steam blasting,sonication). Improving the solubility of the products can improve theefficiency of subsequent solution-based treatment steps. By improvingthe efficiency of other processing steps (e.g., cracking and/orhydrotreatment of bitumen, vaporization of oil shale), the overallenergy consumed in processing the raw materials can be reduced, makingextraction and processing of the raw materials economically feasible.

In certain embodiments, ion beams can be particularly efficient atprocessing raw hydrocarbon-containing materials. For example, due to theability of ion beams to initiate both polymerization anddepolymerization reactions, to deposit heat in the irradiated material,and to sputter or otherwise displace atoms of the irradiated material,hydrocarbon materials such as oil sands, oil shale, crude oil, asphalt,and other materials can be treated to improve additional processingsteps for these materials and/or to extract useful products from thematerials.

Products derived from processing hydrocarbon-containing materials caninclude one or more compounds suitable for use as fuels. The fuelcompounds can be used on-site (e.g., combusted to generate electricalpower) and/or can be transported to another facility for storage and/oruse.

Processing of Crude Oil

The methods and systems disclosed herein can be used to process crudeoil in addition to, or as an alternative to, conventional oil refiningtechnologies. In particular, ion beam treatment methods—alone or incombination with any of the other methods disclosed herein—can be usedfor low temperature oil cracking, reforming, functionalization, andother processes.

Generally, treatment of crude oil and/or components thereof using themethods disclosed herein (including, for example, ion beam treatment,alone or in combination with one or more other methods) can be used tomodify molecular weights, chemical structures, viscosities,solubilities, densities, vapor pressures, and other physical propertiesof the treated materials. Typical ions that can be used for treatment ofcrude oil and/or components thereof can include protons, carbon ions,oxygen ions, and any of the other types of ions disclosed herein. Inaddition, ions used to treat crude oil and/or its components can includemetal ions; in particular, ions of metals that catalyze certain refineryprocesses (e.g., catalytic cracking) can be used to treat crude oiland/or components thereof. Exemplary metal ions include, but are notlimited to, platinum ions, palladium ions, iridium ions, rhodium ions,ruthenium ions, aluminum ions, rhenium ions, tungsten ions, and osmiumions.

In some embodiments, multiple ion exposure steps can be used. A firstion exposure can be used to treat crude oil (or components thereof) toeffect a first change in one or more of molecular weight, chemicalstructure, viscosity, density, vapor pressure, solubility, and otherproperties. Then, one or more additional ion exposures can be used toeffect additional changes in properties. As an example, the first ionexposure can be used to convert a substantial fraction of one or morehigh boiling, heavy components to lower molecular weight compounds withlower boiling points. Then, one or more additional ion exposures can beused to cause precipitation of the remaining amounts of the heavycomponents from the component mixture.

In general, a large number of different processing protocols can beimplemented, according to the composition and physical properties of thefeedstock. In certain embodiments, the multiple ion exposures caninclude exposures to only one type of ion. In some embodiments, themultiple ion exposures can include exposures to more than one type ofion. The ions can have the same charges, or different charge magnitudesand/or signs.

In some embodiments, the crude oil and/or components thereof can befunctionalized during exposure to ion beams. For example, thecomposition of one or more ion beams can be selected to encourage theaddition of particular functional groups to certain components (or allcomponents) of a crude oil feedstock. One or more functionalizing agents(e.g., ammonia) can be added to the feedstock to introduce particularfunctional groups. By functionalizing the crude oil and/or componentsthereof, ionic mobility within the functionalized compounds can beincreased (leading to greater effective ionic penetration duringexposure), and physical properties such as viscosity, density, andsolubility of the crude oil and/or components thereof can be altered. Byaltering one or more physical properties of the crude oil and/or crudeoil components, the efficiency and selectivity of subsequent refiningsteps can be adjusted, and the available product streams can becontrolled. Moreover, functionalization of crude oil and/or crude oilcomponents can lead to improved activating efficiency of catalysts usedin subsequent refining steps.

In general, the methods disclosed herein—including ion beam exposure ofcrude oil and crude oil components—can be performed before, during, orafter any of the other refining steps disclosed herein, and/or before,during, or after any other steps that are used to refine crude oil. Themethods disclosed herein can also be used after refining is complete,and/or before refining begins. In certain embodiments, the methodsdisclosed herein, including ion beam exposure, can be used to processcrude oil even during extraction of the crude oil from oil fields.

In some embodiments, when crude oil and/or components thereof areexposed to one or more ion beams, the exposed material can also beexposed to one or more gases concurrent with ion beam exposure. Certaincomponents of crude oil, such as components that include aromatic rings,may be relatively more stable to ion beam exposure than non-aromaticcomponents. Typically, for example, ion beam exposure leads to theformation of reactive intermediates such as radicals from hydrocarbons.The hydrocarbons can then react with other less reactive hydrocarbons.To reduce the average molecular weight of the exposed material,reactions between the reactive products and less reactive hydrocarbonslead to molecular bond-breaking events, producing lower weight fragmentsfrom longer chain molecules. However, more stable reactive intermediates(e.g., aromatic hydrocarbon intermediates) may not react with otherhydrocarbons, and can even undergo polymerization, leading to theformation of heavier weight compounds. To reduce the extent ofpolymerization in ion beam exposed crude oil and/or crude oilcomponents, one or more radical quenchers can be introduced during ionbeam exposure. The radical quenchers can cap reactive intermediates,preventing the re-formation of chemical bonds that have been broken bythe incident ions. Suitable radical quenchers include hydrogen donorssuch as hydrogen gas.

In certain embodiments, reactive compounds can be introduced during ionbeam exposure to further promote degradation of crude oil and/or crudeoil components. The reactive compounds can assist various degradation(e.g., bond-breaking) reactions, leading to a reduction in molecularweight of the exposed material. An exemplary reactive compound is ozone,which can be introduced directly as a gas, or generated in situ viaapplication of a high voltage to an oxygen-containing supply gas (e.g.,oxygen gas, air) or exposure of the oxygen-containing supply gas to anion beam and/or an electron beam. In some embodiments, ion beam exposureof crude oil and/or crude oil components in the presence of a fluid suchas oxygen gas or air can lead to the formation of ozone gas, which alsoassists the degradation of the exposed material.

Prior to and/or following distillation in a refinery, crude oil and/orcomponents thereof can undergo a variety of other refinery processes topurify components and/or convert components into other products, forexample catalytic cracking, alkylation, catalytic reforming andisomerization, and catalytic hydrocracking. The methods described hereincan be integrated with such refinery processes if desired.

For example, the methods disclosed herein can be used before, during,and/or after catalytic cracking to treat components of crude oil. Inparticular, ion beam exposure (alone, or in combination with othermethods) can be used to pre-treat feedstock prior to injection into theriser, to treat hydrocarbons (including hydrocarbon vapors) duringcracking, and/or to treat the products of the catalytic crackingprocess.

Cracking catalysts typically include materials such as acid-treatednatural aluminosilicates, amorphous synthetic silica-aluminacombinations, and crystalline synthetic silica-alumina catalysts (e.g.,zeolites). During the catalytic cracking process, components of crudeoil can be exposed to ions from one or more ion beams to increase theefficiency of these catalysts. For example, the crude oil components canbe exposed to one or more different types of metal ions that improvecatalyst activity by participating in catalytic reactions.Alternatively, or in addition, the crude oil components can be exposedto ions that scavenge typical catalyst poisons such as nitrogencompounds, iron, nickel, vanadium, and copper, to ensure that catalystefficiency remains high. Moreover, the ions can react with coke thatforms on catalyst surfaces to remove the coke (e.g., by processes suchas sputtering, and/or via chemical reactions), either during cracking orcatalyst regeneration.

The methods disclosed herein can be used before, during, and/or afteralkylation to treat components of crude oil. In particular, ion beamexposure (alone, or in combination with other methods) during alkylationcan assist the addition reaction between olefins and isoparaffins. Insome embodiments, ion beam exposure of the crude oil components canreduce or even eliminate the need for sulfuric acid and/or hydrofluoricacid catalysts, reducing the cost and the hazardous nature of thealkylation process. The types of ions, the number of ion beam exposures,the exposure duration, and the ion beam current can be adjusted topreferentially encourage 1+1 addition reactions between the olefins andisoparaffins, and to discourage extended polymerization reactions fromoccurring.

In catalytic reforming processes, hydrocarbon molecular structures arerearranged to form higher-octane aromatics for the production ofgasoline; a relatively minor amount of cracking occurs. Duringreforming, the major reactions that lead to the formation of aromaticsare dehydrogenation of naphthenes and dehydrocyclization of paraffins.The methods disclosed herein can be used before, during, and/or aftercatalytic reformation to treat components of crude oil. In particular,ion beam exposure (alone, or in combination with other methods) can beused to initiate and sustain dehydrogenation reactions of naphthenesand/or dehydrocyclization reactions of paraffins to form aromatichydrocarbons. Single or multiple exposures of the crude oil componentsto one or more different types of ions can be used to improve the yieldof catalytic reforming processes. For example, in certain embodiments,dehydrogenation reactions and/or dehydrocyclization reactions proceedvia an initial hydrogen abstraction. Exposure to negatively charged,basic ions can increase the rate at which such abstractions occur,promoting more efficient dehydrogenation reactions and/ordehydrocyclization reactions. In some embodiments, isomerizationreactions can proceed effectively in acidic environments, and exposureto positively charged, acidic ions (e.g., protons) can increase the rateof isomerization reactions.

Catalysts used in catalytic reformation generally include platinumsupported on an alumina base. Rhenium can be combined with platinum toform more stable catalysts that permit lower pressure operation of thereformation process. Without wishing to be bound by theory, it isbelieved that platinum serves as a catalytic site for hydrogenation anddehydrogenation reactions, and chlorinated alumina provides an acid sitefor isomerization, cyclization, and hydrocracking reactions. In general,catalyst activity is reduced by coke deposition and/or chloride lossfrom the alumina support. Restoration of catalyst activity can occur viahigh temperature oxidation of the deposited coke, followed bychlorination of the support.

In some embodiments, ion beam exposure can improve the efficiency ofcatalytic reformation processes by treating catalyst materials duringand/or after reformation reactions occur. For example, catalystparticles can be exposed to ions that react with and oxidize depositedcoke on catalyst surfaces, removing the coke and maintaining/returningthe catalyst in/to an active state. The ions can also react directlywith undeposited coke in the reformation reactor, preventing depositionon the catalyst particles. Moreover, the alumina support can be exposedto suitably chosen ions (e.g., chlorine ions) to re-chlorinate thesurface of the support. By maintaining the catalyst in an active statefor longer periods and/or scavenging reformation by-products, ion beamexposure can lead to improved throughput and/or reduced operating costsof catalytic reformation processes.

The methods disclosed herein can be used before, during, and/or aftercatalytic hydrocracking to treat components of crude oil. In particular,ion beam exposure (alone, or in combination with other methods) can beused to initiate hydrogenation and/or cracking processes. Single ormultiple exposures of the crude oil components to one or more differenttypes of ions can be used to improve the yield of hydrocracking bytailoring the specific exposure conditions to various process steps. Forexample, in some embodiments, the crude oil components can be exposed tohydride ions to assist the hydrogenation process. Cracking processes canbe promoted by exposing the components to reactive ions such as protonsand/or carbon ions.

In certain embodiments, ion beam exposure can improve the efficiency ofhydrocracking processes by treating catalyst materials during and/orafter cracking occurs. For example, catalyst particles can be exposed toions that react with and oxidize deposits on catalyst surfaces, removingthe deposits and maintaining/returning the catalyst in/to an activestate. The crude oil components can also be exposed to ions thatcorrespond to some or all of the metals used for hydrocracking,including platinum, palladium, tungsten, and nickel. This exposure tocatalytic ions can increase the overall rate of the hydrocrackingprocess.

A variety of other processes that occur during the course of crude oilrefining can also be improved by, or supplanted by, the methodsdisclosed herein. For example, the methods disclosed herein, includingion beam treatment of crude oil components, can be used before, during,and/or after refinery processes such as coking, thermal treatments(including thermal cracking), hydroprocessing, and polymerization toimprove the efficiency and overall yields, and reduce the wastegenerated from such processes.

Other embodiments are within the scope of the following claims.

1. A method of processing a carbohydrate-containing material, the methodcomprising: irradiating a combination formed by combining acarbohydrate-containing material with an inorganic material.
 2. Themethod of claim 1 wherein irradiation is performed with acceleratedparticles.
 3. The method of claim 2 wherein the particles compriseelectrons accelerated to a speed of greater than seventy five percent ofthe speed of light.
 4. The method of claim 1, wherein thecarbohydrate-containing material comprises a cellulosic orlignocellulosic.
 5. The method of claim 1, wherein combining thecarbohydrate-containing material with the inorganic material comprisesdry blending or co-comminuting.
 6. The method of claim 5, whereincombining the carbohydrate-containing material and the inorganicmaterial comprises co-comminuting the materials while each material iscooled to a temperature below 25° C.
 7. The method of claim 6 whereinthe materials are cooled to a temperature at or below 0° C.
 8. Themethod of claim 1, wherein the inorganic material comprises a metal or ametal alloy.
 9. The method of claim 8, wherein the metal or metal alloyis selected from the group consisting of ferrous metals, base metals,noble metals, precious metals, and transition metals.
 10. The method ofclaim 8, wherein the inorganic material comprises aluminum metal. 11.The method of claim 1, wherein the inorganic material comprises ametallic compound.
 12. The method of claim 11, wherein the metalliccompound comprises iron or cobalt in the 2+ or 3+ oxidation state. 13.The method of claim 1, wherein the inorganic material comprises arefractory material.
 14. The method of claim 13, wherein the refractorymaterial is selected from the group consisting of zircon, fireclay,silica, alumina, chromite, silicon carbide, carbon, mulitite, dolomiteand magnesite.
 15. The method of claim 1, wherein the inorganic materialcomprises a ceramic.
 16. The method of claim 15 wherein the ceramic isselected from the group consisting of oxides, carbides, borides,nitrides, silicides and kaolins.
 17. The method of claim 1, wherein theinorganic material comprises water that is capable of leaving theinorganic material at elevated temperatures.
 18. The method of claim 1,wherein the inorganic material does not have a melting point.
 19. Themethod of claim 1, wherein the inorganic material has a melting point ofgreater than about 400° C.
 20. The method of claim 1, wherein theinorganic material has a specific heat capacity Cp of less than about1.5.
 21. The method of claim 1, wherein the inorganic material has aconductivity of between about 0.004 and about 450 W/mK.
 22. The methodof claim 1, wherein the inorganic material has a density of greater thanabout 1.5 g/cm³.
 23. The method of claim 1, wherein the inorganicmaterial comprises particles having an average particle size of fromabout 0.1 micron to about 100 microns.
 24. The method of claim 1,wherein the combination includes about 0.05 to about 35 percent byweight inorganic material.
 25. The method of claim 1, furthercomprising, after irradiating, removing the inorganic material, andconverting the irradiated carbohydrate-containing material to a productusing an enzyme and/or a microorganism.
 26. The method of claim 25wherein the product comprises ethanol.
 27. The method of claim 25wherein removing takes place after converting.
 28. The method of claim25 wherein the microorganism comprises a yeast.
 29. A method ofprocessing a hydrocarbon-containing material, the method comprising:irradiating a combination formed by combining a hydrocarbon-containingmaterial with an inorganic material.
 30. The method of claim 29 whereinthe hydrocarbon-containing material is selected from the groupconsisting of tar or oil sands, oil shale, crude oil, bitumen, coal,petroleum gases, liquefied natural and/or synthetic gas, and asphalt.31. The method of claim 29 wherein the hydrocarbon-containing materialcomprises a solid, particulate, powder, liquid, gas or combinationsthereof.
 32. The method of claim 31 wherein the solid comprises coal.33. The method of claim 31 wherein the liquid comprises coal.